Basic dyestuffs containing a quaternized pyridine or quinoline radical

ABSTRACT

Basic azo-dyestuffs containing a quaternized pyridine- or quinoline carbonyloxy- or carbonylimino-radical bound to an aromatic nucleus directly or via an alkylene-, alkylene- oxy- or alkyleneimino bridge.

United States Patent Ramanathan et al.

[ 1 Aug. 29, 1972 [54] BASIC DYESTUFFS CONTAINING A QUATERNIZED PYRIDINEOR QUINOLINE RADICAL [63] Continuation-impart of Ser. No. 520,863, Jan.

17, 1966, abandoned.

[30] Application Priority Data Jan. 18, 1965 Switzerland ..674/65 [52]U.S. Cl. ..260/156, 260/146 R, 260/155, 260/158, 260/163, 260/206,260/239.8,

260/240 .1, 260/240 R, 260/287 R, 260/293.69, 260/2948 A, 260/2948 C,

260/2948 F, 260/2943 R, 260/295 AM, 260/2955 '1, 8/41 [51] Int. Cl...C09b 29/36 [58] fieldofselrch ..260/155, 156,146

[56] References Cited UNITED STATES PATENTS 3,501,453 3/ 1970 Steinemann..260/156 1,887,996 11/1932 Conzetti ..260/156 3,148,181 9/1964 Wallaceet a1 ..260/l56 Primary Examiner-Joseph Rebold Assistant Examiner-DonaldM. Papuga Attomey-1-larry Goldsmith, Joseph G. Kolodny and Mario A.Monaco ABSTRACT Basic azo-dyestuffs containing a quaternized pyridineorquinoline carbonyloxyor carbonylimino-radical bound to an aromaticnucleus directly or via an alky1ene-, alkyleneoxyor alkyleneiminobridge.

5 Claims, No Drawings BASIC DYESTUFFS CONTAINING A QUATERNIZED PYRIDINEOR QUINOLINE' RADICAL CROSS-REFERENCES TO RELATED APPLICATION This is acontinuation in part of application Ser. No. 520,863, filed Jan. l7,1966, now abandoned.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is basedon the observation that valuable basic dyestuffs free from acid groupsimparting solubility in water, especially sulphonic and carboxylic acidgroups, and corresponding to the formula wherein A represents theresidue of an organic dyestuff, Z an oxygen atom or an NH- group, X ananion and Y and or 6- membered heterocyclic residue containing aquaternary ammonium group as a cyclic member may be obtained when (a) adyestuff of the formula wherein A and Z have the above meanings and Yrepresents a 5- or 6-membered heterocyclic ring which contains anitrogen atom as a cyclic member, is treated with an alkylating agent;or (b) a dyestuff intermediate containing the residue of the formula isconverted by a suitable reaction, for example by condensation orcoupling, into the dyestuff of the above formula, or (c) a dyestuffcontaining the residue of the formula is acylated with a halide of acarboxylic acid of the formula Particularly suitable starting materialsare dyestuffs of the azo or anthraquinone series; nitro, methine, styryland quinophthalone dyestufis are also suitable. The dyestuff residuesare bound to the heterocyclic residue Y through a carboxylic acid estergroup or a carbamide group. Advantageously OCY represents the residue ofa pyridine carboxylic acid, for example pyridine-2-, -3- or-4-carboxylic acid. The residue OCY may also be derived from one of thefollowing heterocyclic carboxylic acids: quinoline-4- or -8- carboxylicacid, pyrazolone-Zi-carboxylic acid-5, l-phenylpyrazolone-3-carboxylicacid-5, thiazole-Z-carboxylic acid, benzthiazole-2- or -6-carboxylicacid.

The dyestuffs to be used as starting materials may be obtained byacylating a suitable organic dyestufi, especially a disperse dyestuffcontaining an acylatable hydroxyl or amino group, with the halide of aS-membered or 6-membered heterocyclic carboxylic acid that contains anitrogen atom as a cyclic member.

Particularly valuable starting materials are azo dyes, especially thoseof the formula structural formula appears, it refers to the pyridylstructure.

As examples of starting materials for use in the present process thefollowing dyestuffs may be mentioned (in the given formulas --COPyrepresents the residue of pyridine-3- or -4-carboxylic acid):

a. Azo dyes OCH:

The above-mentioned dyestuffs are treated according to this inventionwith alkylating agents, advantageously with alkyl or aralkyl halides orwith the alkyl or aralkyl esters of sulphuric acid or of organicsulphonic acids. As examples of alkylating agents the following may bementioned: Methylchloride, methylbromide or methyliodide,benzylchloride, B- chloropropionic acid methyl ester, B-chloropropionicacid amide, trimethyloxonium borofluoride, dimethyl sulphate, diethylsulphate, benzenesulphonic acid methyl ester and para-toluenesulphonicacid ethyl or butyl ester. Alkylation is advantageously performed byheating in an inert organic solvent, for example in a hydrocarbon e.g.,benzene, toluene or xylene, or in a chlorinated hydrocarbon e.g., carbontetrachloride, tetrachloroethane, chlorobenzene or orthodichlorobenzene,or in a nitrated hydrocarbon e.g., nitromethane, nitrobenzene or anitronaphthalene.

The variant (b) of the present process is particularly suitable for themanufacture of azo dyes. For this purpose a diazotized amine is coupledwith a coupling component, either the diazo or the coupling componentcontaining the residue of the formula Preferred diazo components areamines of the benzene series, and preferred coupling components areaminobenzenes, hydroxybenzenes, aminonaphthalenes, hydroxynaphthalenes,

pyrazolones and acetoacetic arylides. The coupling is carried out inknown manner.

According to variant (c) of the present process a dyestuff that containsan acylatable amino or hydroxyl group, for example one of the dyestuffsmentioned above which contains a hydrogen atom in place of the residue-COPy, is acylated with a halide of a carboxylic acid of the formulapreferably of a quatemated pyridine carboxylic acid, for example withthe chloride of the formula COCl 6 anions of other inorganic acids, forexample the anion of phosphoric or sulphuric acid, or those of organicacids, for example formic, acetic, chloroaceticipxalic, lactic ortartaric acid; in certain cases the free bases may also be used. Thedyestuff salts may also be used in the form of double salts, for examplewith halides of elements of Group 2 of the Periodic Table, especiallyzinc or cadmium chloride.

The dyestuff salts obtained according to this invention are suitable fordyeing or printing a wide variety of materials, for example tannedcellulose fibers, silk, hairs, leather or fully synthetic fibers,especially polyacrylonitrile or polyvinylidene cyanide (Darvan). Thedyeings obtained on these fibers are distinguished by good fastness tolight. The dyestuffs also build up well on polyacrylonitrile fibers andreserve well on wool which makes them particularly suitable for dyeingunion fabrics containing polyacrylonitrile. Over comparable dyestuffsdescribed in US. Pat. No. 2,359,864 the present dyestuff shows thetechnical advantage in that they can also be applyed on polyacrylonitrilfibers at temperatures above 100, for example at 130.

Unless otherwise indicated, parts and percentages in the followingExamples are by weight.

EXAMPLE l 26.7 parts of nicotinic acid chloride hydrochloride are addedat 0to 5C to a solution of 21.67 parts of 4'-N,N-dihydroxyethyl-amino-2,2', 6-trichloro-4- nitroazobenzene in partsof pyridine. The batch is slowly heated and stirred for 3 hours at aboutC, allowed to cool, poured into ice water and neutralized with sodiumhydroxide solution. The precipitated dyestuff is filtered by suction,rinsed with water and dried.

The dried dinicotinic acid ester is dissolved in parts of chlorobenzene,and a solution of 19 parts of dimethyl sulphate in l00 parts ofchlorobenzene is added. The mixture is stirred for about 5 hours at 80Cand then cooled. The chlorobenzene layer is separated. The residue isdissolved in water and the product is salted out with sodium chlorideand zinc chloride. The precipitated dyestuff of the formula Cl Cl CH3 isfiltered by suction and dried; it dyes polyacrylonitrile fibers brownshades having very good properties of fastness.

DYEING INSTRUCTIONS 1 part of the dyestuff obtained as above isdissolved in 500 parts of water with addition of 2 parts of 40 per centacetic acid. 100 parts of dried yarn from polyacrylonitrile staplefibers are immersed in this bath at 60C, the temperature is raisedwithin half an hour to 100C and the yarn is dyed for 1 hour at the boil.The dyeing is then thoroughly rinsed and dried. The resulting brownshade displays very good fastness to light, sublimation and washing.

EXAMPLE 2 13.4 parts of nicotinic acid chloride hydrochloride are addedat 0to 5C to a solution of 18.2 parts of 4',N-hydroxyethyl-N-cyanoethylamino-Z-cyarm-4- nitroazobenzene in 75 partsof pyridine. The batch is slowly heated and stirred for 3 hours at about80C, allowed to cool, poured into ice water and neutralized with sodiumhydroxide solution. The precipitated dyestuff is suction-filtered,washed with water and dried.

The dried mono-nicotinic acid ester is dissolved in 250 parts ofchlorobenzene and a solution of 9.5 parts of dimethyl sulphate in 50parts of chlorobenzene is added. The mixture is stirred for about 5hours at 80C and then cooled. The chlorobenzene layer is separated. Theresidue is dissolved in water and the product salted out with sodiumchloride and zinc chloride. The precipitated dyestuff of the formula issuction-filtered and dried; it dyes polyacrylonitrile fibers red-brownshades having very good properties of fastness.

in column I of the following Table more dyestufis are listed which maybe reacted as described above with the alkylating agent shown in columnII to give further 20 azo dyestuffs in accordance with the invention.The

shades obtained with the resulting dyestuffs on polyacrylonitrile fibersare listed in column HI:

No. 1 11 1 u 1 ON (011;)!304 Brown.

N 0:NN=NN(CII:CI1=0CO 2 C1 (CIhhSOt Scarlet.

I clncmcN cnlcino C00 3 Cl (C [13):804 DO.

I cnnoN mmo(m 4 i (ll n-(hllallr Ruby (I l 1 b llXl.

5 Cl Scarlet.

1 cnncN Gll:C -S0nllz cnno 0 0- 6 CzII-|CN Brown.

/ -Cn,c1

cilno c o- 1 l. /(JH5 (cumsoi Scarlet.

K 4 0 F3 (CgllghSO Rld.

l Cllz olN-- -N N -N No. I 11 III 30 (ll OH (CHahSOi D0.

N -c OHN- N-N EXAMPLE 3 l5 EXAMPLE 4 9.35 parts of nicotinyl chloridehydrochloride are 26.7 parts of isonicotinic acid chloride hydrochlorideslowly added in portions while stirring at about 20C to are added at to5C to a solution of 13.55 parts of 4 a mixture of 15.85 parts ofl,4-diamino-2-bromo-[N,N-bis-(2'-hydroxyethyl)-amino]2-methylbenzyanthraquinone in 4l partsof N-methylpyrrolidone, and

lidene malonitrile in 75 parts of pyridine. The mixture is slowly heatedand stirred for 3 hours at about 80C, then cooled, poured into ice waterand neutralized with sodium hydroxide solution. The precipitateddyestuff is suction-filtered, washed with water and dried.

The dried diisonicotinic acid ester is dissolved in 100 parts ofchlorobenzene and a solution of 19 parts of dimethyl sulphate in 100parts of chlorobenzene is added, the mixture is stirred for about 5hoursat 80C and then cooled. The chlorobenzene layer is separated, theresidue dissolved in water and the product salted out with sodiumchloride and zinc chloride. The precipitated dyestuli of the formulaCHsBOF the reaction mixture is then stirred for 6 hours. The batch isdiluted with water and the precipitated dyestufi suction-filtered. Thefilter cake is suspended in water, rendered faintly alkaline with sodiumcarbonate solution, stirred, filtered once more, rinsed with water anddried.

The dried product is dissolved in 125 parts of nitrobenzene and asolution of 9.5 parts of dimethyl sulphate in 50 parts of nitrobenzeneis added. The mixture is stirred for about 5 hours at C and then cooled.The nitrobenzene layer is separated and the residue dissolved in hotwater, filtered and the filtrate is salted out with sodium chloride. Theprecipitated dyestuff of the formula NHgBr is filtered and dried; itdyes polyacrylonitrile fibers redviolet shades having very goodproperties of fastness.

in column I of the following table further dyestuffs are listed whichmay be treated as indicated above with the alkylating agent of column IIto give further dyestuffs in accordance with the invention. Theresulting dyestuffs produce on polyacrylonitrile fibers the shades shownin column Ill.

No. I II III 1 Dlmethyl- Greenish NC CHgCHaO CO sulphate. yellow.

N /C=HC N\ N C I OHiCHiO C 0 2 NC CzHs do D0.

C=I C -N NC CIhCHaOCO NO. I II III 1 1111-12 HzOzsoi Violet.

Nr1c0- 2 (l) 1TH; Same as above u. Red-violet.

W 0CH:

O NHCO 3 /O\ (3H .do Orange.

NHOo

4 (H) ()H .....de Blue.

N 0 NH-N1ic0- 5 0 NH: -Udo r. Ruby red.

II N O:( O-0c,H.oc0-

O OH

6 CO 00 .d0 Violet.

NH NH ('10 CO N G EXAMPLE 5 is filtered and dried; it dyespolyacrylonitrile fibers yellow shades having excellent properties offastness.

EXAMPLE 6 A hydrochloric acid solution of 21.3 parts of 4-nicotinylaminoaniline is diazotized with sodium nitrite and coupled at10C in a solution, rendered alkaline with sodium carbonate, with 10.8parts of l-hydroxy-4- methylbenzene. The dyestufi formed is separatedand dried.

The dyestufl is dissolved at 1 10C in 500 parts of anhydrouschlorobenzene and 12.6 parts of dimethyl sulphate are added dropwisewithin 15 minutes at this temperature. The batch is then stirred for lV: hours at l20to C and allowed to cool, whereupon the quaternateddyestufl' precipitates quantitatively; it is separated, dissolved in1,500 parts of hot water, stirred I OH;

forms a yellow, water-soluble powder which dyes polyacrylonnitrilefibers brilliant yellow shades which are very fast to light.

Dyestuffs that color polyacrylonitrile fibers similar shades of equallygood fastness to light are obtained by using as coupling componentl-hydroxy-4-cyclohexylbenzene, l-hydroxy-4 phenylbenzene, l-hydroxy-4-tertiary butylbenzene or l-hydroxy-4- acetylaminobenzene instead ofl-hydroxy-4-methylbenzene.

When the diazo compounds of the amines listed in column l of the tablebelow are coupled in the same manner with coupling components mentionedin column Il and the resulting azo dyestuffs are quaternated with thealkylating agents mentioned in column "I, dyestuffs are obtained whichhave similar fastness properties and dye acrylonitrile fibers the shadesindicated in column IV.

hydrochloric acid. The batch is clarified by filtration through activecarbon and the pure dyestuff is salted out from the filtrate with sodiumchloride, filtered, washed with ice water and dried. The resultingdyestufi of the formula onI T+--u1- l Cl forms a yellow powder whichdyes polyacrylonitrile fibiers brilliant yellow shades of excellentfastness to lig t.

A dyestufl that also dyes polyacrylonitrile fibers brilliant yellowshades of excellent fastness to light is also obtained when4-(N-ethylnicotinylarnino)-aniline hydrochloride is used as diazocomponent.

EXAMPLE 8 24.3 parts of 2-hydroxy-5-amino-4'-methoxy-l,l' azobenzene aredissolved by healing in 200 parts of pyridineand 14.2 parts of nicotinylchloride are added within 10 minutes at C. The batch is stirred foranother lizhouis at 80to C and then allowed to cool. The reaction massis slowly dropped into L000 parts of water and the precipitated dyestufiis isolated and dried. g

The new dyestufi is dissolved at 1 10C in 200 parts of drydimethylforrnamide and 12.6 parts of dimethyl III IV (0}IJJ2SOI Yellow.

O-smcm EXAMPLE 7 26.35 parts of 4-(N-methylnicotinylamino)-anilinechloride are diazotized and coupled at 0to 5C with 12.85 parts ofl-hydroxy-4-chlorobenzene in a solution rendered alkaline with sodiumcarbonate. The dyestufl' is isolated and dissolved in 1,500 parts ofhot, dilute with a small amount of ice water and dried. The new,

water-soluble dyestufl' of the formula forms a yellow powder which dyespolyacrylonitrile fibers brilliant yellow shades of very good fastnessto light.

Dyestuffs that also dye polyacrylonitrile fibers yellow shades fast tolight are obtained by using as the starting dyestuff 2-hydroxy-5-amino-4'-ethoxy-1 ,l azobenzene, 2-hydroxy-5-amino-4 '-chlorol l azobenzene,2-hydroxy-5 -amino-l '-azobenzene, 4- amino-] ,1 '-azobenzene or4-amino-4-nitro-l ,l azobenzene.

When the azo dyestuffs listed in column I of the Table below are reactedin the same manner with the acid chlorides mentioned in column II, andthe resulting products are quaternated with the alkylating agentsmentioned in column In, dyestuffs are obtained which have similarproperties and dye acrylonitrile fibers the shades indicated in columnIV.

is filtered and dried; it dyes polyacrylonitrile fibers red shadeshaving excellent properties of fastness.

hydroxyethyl-N-B-cyanoethylaniline in l20 parts of pyridine. The mixtureis slowly heated and stirred for 3 hours at about 80C, allowed to cool,poured into ice water and neutralized with sodium hydroxide solution.The precipitated ester is suction-filtered, rinsed with water and dried.

29.5 parts of the dried nicotinic acid ester are dissolved in 200 partsof warm chlorobenzene and a solution of 18.9 parts of dirnethyl sulphatein parts of chlorobenzene is added. The mixture is stirred for 30 about4 hours at 90to 95C and, then cooled. The

III [V COCl OCH: OH

OCHs

Yellow.

CilluBr Do.

(CH3):S04 D0.

EXAMPLE 9 2.66 parts of 5-arnino-3-phenyl-l ,2,4-thiadiazole arediazotized in known manner and coupled with an aqueous solution of 6.32parts of N-B-cyanoethyl-NB-(N- methylnicotinyl)-hydroxyethylanilinemethosulphate. The coupling mixture is rendered neutral to Congo redwith sodium acetate solution. On completion of the coupling the reactionmixture is salted out and filtered. The suction filter cake is dissolvedhot in water, clarified by filtration and once more salted out. Theprecipitated dyestuff of the formula chlorobenzene layer is separatedand the product washed with petroleum ether and dried. The quatemarysalt dissolves completely in water and the solution may be used for thecoupling reaction.

The following table lists a number of further components which yielddyestuffs in accordance with the invention when, as indicated above thediazo component of column I is coupled with the coupling component ofcolumn ll.

N o. Diazo component Coupling component Slimli- L, i i2,6dichloro4-nitroanillne CQILCN l'ulluwish brown.

2 .7 V l z-amino-fi-nitrothiazole w V 7 4 .4 Same as above r V s A t w VV v 2-amino-onitrobenzthiazole .d V V ltnbyrvd.

4., a v. 2-amino-6cyanobenzthialole ..do .i a lml.

5 V V i V e .r 2-chloro-4-nitroaniline C'glhCN (IlIu Rod.

| C;lI ()C0-- CH:

6 i. 5-amino-3-methy1 1,2 4-thiadiszole O ILCN S arlet.

C1H40CO +N""CH3S0{ 7 Z-amino-b-methylsullonyl thiazole 3 Violet.

CH: CHaS 0 8 2-arnlno-5-cyan0thialole r i /C,HO C H4CN Do.

N 0 Ha s Or oHlcu-oc 0- N C H; C Hz J w l t i v l2-amino-6-methylsullonyl benzthiazole. i 0 11 0 C lhCN Ruby red.

3N c H, s 0 r C IIlO C O l C Us 10.. 4 'Z-nmino-fi-phonyl-l,3,l-thiadiuzolo GHQ-CH1 lied.

/C H: /C H:

NCH:CHZOC O N cmso EXAMPLE 1 0 By using Z-nitraniline,2-nitro-4-chloraniline or 2- 15.2 parts of 3-nitro-4-aminotoluene arediazotized nitrM'methoxyaniline as the dim component dyestuffs areobtained that likewise dye and coupled with 18.9 parts of l-[3--amlnophenyl]-3- methylpyrazolone-(S) in a solution rendered alkalinepolyacrylommle fibers yellow shades whlch are fast to with sodiumcarbonate. i d d t ms a1 btainedb th The dyestuff formed is isolated anddried, reacted cry goo yes u are y usmgas e with nicotinyl chloride asdescribed in Example 8 and coupling mmponem iI4"aminophenyu'3'memyl'uatemated with dimeth l sul hate. x42"aminphenyn'3'methyl' q The new,water-solublz dye tuff of the formula pyrazolone'(s) pyrazolone-(S).

N02 Then the diam compounds of the amines listed in P column I of thetable below are coupled in the same II3CC manner with the couplingcomponents mentioned in N F column II and the resulting compounds areacylated :N/ 1 with the acid chlorides mentioned in column III, and

Q the am dyestuffs so obtained are finally quaternated with thealkylating agents mentioned in column IV, forms a yellow powder whichdyes polyacrylonitrile dyestuffs are obtained which have similarproperties fibers brilliant yellow shades having very good fastness 5and dye acrylonitrile fibers the shades shown in column to light. V.

17.25 parts of 2-chloro-4-nitraniline are diazotized and coupled with26.4 parts of l-nicotinylamino-7- hydrox naphthalene in a solutionrendered alkaline with so mm carbonate. The dyestuff formed is isolated,

dried and quaternated in the usual manner in chlorobenzene with dimethylsulphate.

The new, water-soluble dyestuff of the formula forms a brown powderwhich dyes polyacrylonitrile fibers scarlet shades of very good fastnessto light.

By using as the diazo component 2-amino-5- nitrophenyl-methyl-sulphone,2-amino-4-nitrotoluene, 2- or 4- nitraniline or 2-nitro-4-chloraniline,dyestuffs are obtained which have equally good properties.

EXAMPLE 12 21.75 parts of 4.6-dinitro-2-chloraniline diazotized andcoupled with 30 parts of 2-(N- cliethylamino-4-nicotinylamino-anisole)in an acetic acid solution. The dyestufi' formed is isolated, dried andquaternated with dimethyl sulphate in nitrobenzene.

The new, water-soluble dyestufi of the formula forms a dark powder whichdyes polyacrylonitrile fibers reddish blue shades which are very fast tolight. 5

By using 2-nitro-4-chloraniline, 2-cyano-4- nitraniline or4,6-dinitrol-2-bromaniline as the diazo component, dyestuffs areobtained which have the are 50 Very good dyestuffs are also obtained byusing as coupling component 2-(N-dimethylamino)-4- nicotinylaminoanisoleor Z-(Nfi-cyanoethyl-N- methylamino)-4-nicotinylaminoanisole.

EXAMPLE 13 38.4 parts of Z-nitrodiphenylamine-4-sulphonic acid-4'-amino-anilide in 200 parts of pyridine are mixed at to C with 19.2parts of nicotinylchloride-N- methylchloride and the batch is stirredfor 3 hours at 80to 85C. The batch is poured into 1,000 parts of water,hydrochloric acid is added to obtain an acid reaction to Congo red andthe whole is filtered hot with active carbon. The dyestuff is salted outof the filtrate with sodium chloride, isolated and dried under vacuum.

The new, water-soluble dyestufi' of the formula acid is added to thefiltrate until an acid reaction to Congo is obtained and it is thenevaporated in a rotary evaporator.

The finely comminuted, dust-dry product is added at room temperature to20 parts of thionyl chloride, and while stirring vigorously thetemperature is raised within 20 minutes from 20to 68C, whereupon theproduct dissolves, accompanied by a strong evolution of sulphur dioxideand hydrogen chloride gas. When the evolution of gases ceases, theexcess thionyl chloride is distilled ofi'. Nicotinylchloridemethylchloride settles out as a waxy, white substance which can be useddirectly.

EXAMPLE 14 30.4 parts of 3-hydroxy-4aminoquinophthalone in 300 parts ofpyridine are mixed at 80to 85C with 19.2 parts ofnicotinyl-chloride-N-methylchloride and the batch is stirred for 3 hoursat 80to 85C, then poured into 1,200 parts of water; hydrochloric acid isadded until an acid reaction to Congo red is obtained and the whole isfiltered hot through active carbon. The dyestuff is salted out of thefiltrate with sodium chloride, suction-filtered and dried under vacuum.

The new, water-soluble dyestutf of the formula H 0 o w (a Nnb- C1 \N \C/l forms a yellow powder which dyes polyacrylonitrile fibers yellowshades which are very fast to light.

Dyestuffs have equally good properties are obtained by reacting3-hydroxy-3aminoquinophthalone or 3,4dihydroxyquinophthalone withnicotinylchloride- N-methylchloride.

We claim: 1. A basic azo-dyestuff free from sulfonic and carboxylic acidgroups, in which the cation corresponds to the formula wherein D isselected from the group consisting of thiazolyl, benzthiazolyl,thiadiazolyl, thiazolyl substituted by nitro, methylsulfonyl or cyano,benzthiazolyl substituted by nitro, cyano, methylsufonyl or chloro,thiadiazolyl substituted by methyl or phenyl and substituted benzenewherein the substituents are selected from the group consisting ofchloro, bromo, cyano, nitro, phenylazo, lower alkyl, lower alkoxy,tn'fluoromethyl, carbalkoxy, lower alkylsulphonyl, lowerN-alkylsulfonamide and A is lower alkylpyrazolone, phenyl-pyrazolone,hydroxynaphthalene, 4-hydroxy-N-alkylquinolone, or benzene orsubstituted benzene wherein the substituent is selected from the groupconsisting of chloro, bromo, hydroxy, lower alkyl, lower alkoxy, loweralkanoylamino, lower alkylamino, phenyl or cyclohexyl, p is CO, SO,, ora direct linkage, q is oxygen, imino or a direct linkage, r is loweralkyl-, phenyl, methylphenyl, benzyl or may also be a direct linkage ifp and q are also direct linkages, Y is unsubstituted quatemized pyridineor quinoline bound to CO via a ring carbon atom, Z is a member of thegroup of oxygen, imino, N-methylimino, N-phenylimino and n is l or 2,and in which dyestuff the anion is selected from the group consisting ofsulfate, phosphate, sulfonate, bromide, chloride, iodide, C alkylcarboxylic acid, ZnCl, and CdCl, and "lower" means including up to fourcarbon atoms."

2. A basic azo dyestuif of the formula r l u in which X, represents amember selected from the group consisting of hydrogen, chlorine,bromine, cyano, lower carbalkoxy, lower alkylsulfonyl, phenylazo andnitro, Y, is a member selected from the group consisting of hydrogen,chlorine, bromine, lower alkyl, lower alkoxy, trifluoromethyl, lowercarbalkoxy, cyano and nitro, Z, is a member selected from the groupconsisting of hydrogen, chlorine and bromine, at least one of theradicals X, and Y, standing for a member selected from the groupconsisting of a nitro, lower carbalkoxy, cyano, lower alkylsulfonyl andphenylazo, V represents a member selected from the group consisting ofhydrogen, chlorine, bromine, lower alkyl, lower alkoxy and loweralkanoylamino, W is a member selected from the group consisting ofhydrogen, lower alkyl, lower alkoxy, R represents an alkyl,carbalkoxyethyl, cyanoethyl and lower alkoxyalkyl and X is an anionselected from the group consisting of sulfate, phosphate, sulfonate,bromide, chloride, iodide, C alkyl carboxylic acid, ZnCl, and CdCl,.

3. The dyestuff of the formula oi-nomoN 4. The dyestufi of the formula U1120 IIzCN 5. The dyestufi of the formula OzN- UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 3,I'J Dated Augus 97 or(s)VISVANATHAN I-IAI/LAI-IA'II-IAII ET AL Invent It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Cover page, after the Inventors and before "[221 insert Assignors toCIBA'GEIGY Ardsley, N.Y. a corporation of New York Signed and sealedthis 6th day of August 197 SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,687.929Dated August 1972 Patent No.

Visvanathan Ramanathan et a1 .1 Inventor(s) that error appears in theabove-identified patent It is certified and that said Letters Patent arehereby corrected as shown below:

On the cover sheet insert [73] Assignee: Ciba-Ceigy AG, Basle,Switzerland This certificate supersedes Certificate of Correction issuedAug. 6, 1974.

Signed and sealed this 26th day of November 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

2. A basic azo dyestuff of the formula
 3. The dyestuff of the formula
 4. The dyestuff of the formula
 5. The dyestuff of the formula 